Water-insoluble azo dyestuffs



, v 2,941,992 WATER-INSOLUBLE AZO DYESTUFFS Paul Rhyner and Hugo Illy, Basel, Switzerland, assignors to Ciba Limited, Basel, Switzerland, a Swiss firm No Drawing. Filed Sept. 29, 1958, Ser. No. 763,826 Claims priority, application Switzerland Oct. 11, 1,957

1 Claim. (Cl. 260-205) The present invention provides valuable new azo-dye- United States Patent C stufis which are free from acid groups imparting solubility in water and correspond to the general formula AN=N-B in which A represents a benzene radical of the formula in which X represents a hydrogen or halogen atom or a nitro, cyano, alkyl-sulfone, sulfonamide or carbalkoxy group, Y represents a hydrogen or halogen atom or an ,alleyl, alkoxy, nitro, cyano, alkyl-fsulfone, sulfonamideor carbalkoxy group, Z has one of the meanings given for XQM;

, 1-amino-4-methylbenzene,

j 1-amino-4-chlorobenzene,

; 1-amino-4-bromobenzene,

l-amino-4-methylsulfonylbenzene, j.1-amino-benzene-4-carboxylic acid methyl ester, 1-aminobenzene-4-chloromethylsulfone,

' l-amino-benzene-4-cyanoethylsulfone,

l-amino-Z 4-dichlorobenzene,

1-amino-2-methyl-4-chlorobenzene,

' l*amino-2-trifiuoromethyl-4-chlorobenzene, 'l-amino-4chloro-2-methylsulfonylbenzene, l-amino-Z-chloro-4-methylsulfonylbenzene,

.1-amino2-chloro-4-chloromethylsulfonylbenzene, 1-amino-2-chloro-4-cyanoethylsulfonylbenzene,

' l-amino-Z: 4-bis (methylsulfonyl) -benzene, ,1-amino-2 6-dibromo-4-methylsulfonylbenzene,

when X is a hydrogen or halogen atom or a cyano,

Patented June 21, 1960 "ice 2 1-amino-2-methyl-4-nitrobenzene, 1-amino-2-methoxy-4-nitrobenzene, 1-amino-Z-trifiuoromethyl-4-nitrobenzene, l-amino-2-methylsulfonyl-4-nitrobenzene, 1-amino-2-chloromethylsulfonyl-4-nitrobenzene, l-amino-2-cyanoethylsulfonyl-4-nitrobenzene, l-amino-Z:4-dinitrobenzene, 1-amino-2 4- dinitro-6 -chlorob enzene, l-amino-2:4-dinitro-6-bromobenzene.

Of special interest are aminobenzenes that contain at least one cyano group bound to the benzene nucleus such, for example, as

1-amino-4-cyanobenzene, 1-amino-2-chloro-4-cyanobenzene, -1-amino-2-cyano-4-chlorobenzene, l-amino-Z:4-dicyanobenzene, 1-amino-2-cyano-4-methylsulfonylbenzene, 1-amino-4-cyano-2-methylsulfonylbenzene, 1-amino-2-cyano-4-nitrobenzene.

Advantageous coupling components are amines of the formula CHaQHaCN ornorno-N l in which R represents a hydrogen or halogen atom or an alkyl, alkoxy or aliphatic acylamino group, and k represents a hydrogen atom or an alkyl'or alkoxy group.

Examples of suitable coupling components are:

N-bis-cyanoethyl aniline, l-(N-bis-cyanoethyl)-amino-3-methylbenzene, 1-(N-bis-cyanoethyl)-amino-3-methoxybenzene, 1-(N-bis-cyanoethyl)-amino-3-acetylaminobenzene, l-(N-bis-cyanoethyl)-amino-3-chlorobenzene,

1- (N-bis-eyanoethyl) -amino-2 5 -dimethylbenze ne, 1 (N-bis-cyanoethyl)-amino-Z-methoxy-S-methylbenzene.

The aforesaid coupling components are either known compounds or can be made by methods in themselves known, for example, by reacting an appropriate bischlorethyl compound with an alkali metal cyanide (J. Chem. Soc. 1934, page 1536), or by reacting an appropriate aniline with acrylonitrile.

The amines to be used as diazo-components can be diazotised by methods in themselves known, for example, with the aid of a mineral acid, more especially hydrochloric acid, and sodium nitrite, or with a solution of nitrosyl-sulfuric acid in concentrated sulfuric acid.

The coupling can also be carried out by a method in itself known, for example, in a neutral to acid medium, if desired in the presence of sodium acetate or a similar buffer substance capable of regulating the speed of coupling or of a catalyst such as pyridine, or a salt thereof.

After the coupling reaction the dyestufis formed can easily be separated from the coupling mixture, for example, by filtration, since they are substantially insoluble in water.

The monoazo-dyestuffs of this invention are excellently suitable for dyeing or printing structures, for example, made from polyamides, and more especially of fibers of cellulose acetate rayon, of cellulose triacetate and of polyethylene terephthalate.

The dyeings produced with the new dyestuffs on the aforesaid structures are distinguished by their pure, vivid tints and by their good general properties of fastness, above all by their good fastness to sublimation and light.

'The following examples illustrate the invention, the parts and percentages being by weight:

acetate the dyestufi is precipitatedas'a brownish red powder which dyes cellulose acetate rayon, nylon, cellulose triacetate and polyester fibers pure red tintsj The dyeings on polyester fibers: are distinguished by' their very good fastnesstoilig htand' sublimation. f 9

V V Eatamplei 2 i ii. 0, O A c zmornoN' OF: v

20.6 parts of l amino-trifluorornethyl-4-nitrobenzene are diazotised as described, in Example 1, and coupled with 19.9 parts of N:Nbis-(cyanoethyl)-aniline. The dyestufi separates as a dark red powder, and dyes fibers ,Of cellulose acetate rayon, nylon, cellulose triacetate and polyesters red tints having the same properties as the 'dyesmfi of Example 1. J

Example 3 1 eugenics:

- i JHzCHzCN 11.8'par'ts of l-amino-4-cyanobenzene are dissolved in 200 parts of 2 n-hydrochloric acid, cooled with ice to 0 to 5 C. and'25 parts of 4'n-sodiun1 nitrite solution are added. The coupling is carried out as described in Example 1. a a

' The dyestufi dyes cellulose acetate, polyamide, celluj: oxide.

lose triacetate and polyester fibers pure yellow tints. The

'dyei ngs on polyester fibers are distinguished by their 'good'fastness to light and sublimation.

' By diazotising amines named in column 1' of the following table, as described in the foregoing examples, and coupling the diam-compounds with the coupling componeutnamed in columnII, dyestufis are obtained that dyed cellulose acetate rayon, polyamide, cellulose triacetate and polyester fibers the tints given in column III.

I II III Diazo component Coupling component Tint I. 1-amino-4-ehlorobenzene Bls-(eyanoethyD-aniline... palle yelow. 2. 1-amlno-2:4-dlchlorobenzene .'.do golden yellow. 3. 1-amlno-2-trifluoromethyld0 yellow.

kchlorobeuzene. 4. 1-amiuo-2.-cyau0-6-ch1orodo bluish 4-m'trobenzene. red. 5. 1 -amino-2-methyl-4-nltrobem do orange.

zene. Y 6. 1-amino-2-methoxy-4-nltrodo Do.

benzene. v 7. 1-amino-2-trifluoromethyl-4- -..do red.

nitrobenzene, 8. 2-amino-5-nitro-benzoic acid in Do. methyl ester. 9,'1 amino-2-methylsulfoue4-nido;- 4-.-.-- Do. -trobenzene. v 10. l-amlnobenzenei-methyl- ..do yellow. sulfone.- 11. 1-aminobenzene-4-chlorodo -J golden methylsulfone. yellow. 12. 1-aminobenzene-4-B-eyano- -.do yellow.

methylsulfone. j 1

By using, instead of the coupling component named in column II, l-di-(cyanoethyl)+amino-3-methylbenzene or 1 di (cyanoethyl) 9 ,3 methyl 6 methoxybenzene, similar dyestufis result.

E P 4 1 1 gram of the dyestufif obtained as described 111 B):- ample 1 ispasted with 1.5 grams of sulfite cellulose Waste 'liquo'r' or'dinaphthyhnethane disulfonicacid'ora condensa'tion product of a fatty alcohol with ethylene oxide, then diluted with Water-to 4000 cc., and there are added, per liter, *1 cc. of acetic acid of 40% strength and 1 gram of a condensation product of'a fatty alcohol with ethylene grams of a yarn of polyester fibers is dyed in the resulting dyebath for /2 to 1 hour at 115 to 132 C. A deep red dyeing of very good fastness tolight and sublimation is obtained. 1 i What is claimed is:

The azo-dyestuff of the formula References Cited in the file of this patent UNITED STATES PATENTS Sartori Feb. 19, 1957 

